Vat dye and process of making same.



ALBRECHT SCEI'IIJ'E, ERNST BEYK, AND ROBERT VOSS, OF HQCHST ON-THE-IVZAIN, v GER-MANY, ASSIGNORS T FARB'WERKE VORM. MEISTER LUCIUS 8c BRUNING, OF HljCHST-QN-THE-MAIN, GERMANY, A CORPORATION OF GERMANY.

VAT DYE AND PROCESS OF MAKING TSAME.

We Drawing.

To (LZZ whom it may concern:

Be it known that we, ihLBRECHT SCHMIDT, Ph. ll, chemist, En s'r Burn, Ph. 1)., chemist, and ROBERT Voss, engineer dipl., citi- Zens of the Empires of Germany and Austriadiinngary, respectively residing at lilochst-on-the-Main, Germany, have invented certa n new and useful Improvements in the manufacture of Vat Dyestutis, of which the following is a specification.

We e found lllttt by treating with a halogen il (or 5-) amino-Sexy-1.-thionaphthene (metaor para-aniino-oxythionaphthene) andisatin or its substitution-products, analogues or the anilids of the isatin substituted in the alpha position, or the acidyl derivatives these condensation-products, new vat dyestalls are obtained, which are distinguished from the primary dyestufi's by a ditlerent shade of color and by greater fastness.

In t iis process the halongeni'zation may be efiected with or without the addition of a dissolving or suspending agent such as concentrated sulfuric acid, water, carbon-tetrachlorid, nitrobenzene or the like. These products have the general formula:

in which It, means H, ncidyl; B -H, halogen hlo NH and R 'H, halogen; being brownish to dark powders, insoluble in. water, alcohol, benzene, ether, dilute acids andallzalies, soluble in concentrated sulfuric acid with a brownish-violet to blue color, and hardly soluble in hot nitrobenzene, anilin and the like, yielding when treated with alkaline reducing agents like hydrosulfite, a yellowish to brown vat from which cotton and wool are dyed very fast yellowishbrown to brown and grayish tints.

The new products'dye cotton and wool in the alkalinevat tints which possess a considerably increased fastness as compared with the dyeings obtainable by the abovementioned non-halogenized dyestuffs.

Example I: grams of the condensationproduct obtainable from i-acetaminophe'nyl- 2-thioglycol-o-carboxylic acid, or meta- Specificajcion of Letters Patent.

-iehcondensation-pmducts from 6- Fatented Aug. 3%, 1910.

Application filed November 17, 1909. Serial No. 528,567.

aminoxythionaphthene, and isatin heated with 150 grams of nitroben-zene and grams of bromin for two hours to 160. After cooling the mass is filtered OE and are the dyestuff washed by boiling it with alcohol. It forms a reddish-brown powder which is diilicultly soluble in most of the solvents and which dyes wool and cotton, in the alkaline vat yellowish-brown tints. The bromination may also be carried out for instance in presence of concentrated sulfuric acid, water, carbon tetrachlorld or the like,

in which case a lower temperature is applied for the broniination.

Example II: 10 grams of the, condensation-pr0duct obtainable from -aceteminophenyl-2-thioglycol-1-carboxylic acid, or meta amino oxythionaphthene, and dibromoisatin are heated with 150 gramvof nitrobenzene and 30 grams of bromin for 2 hours i tion-product obtainable from "tacetaminophenyl 2 thioglycol 1 carboxylic acid, or ineta-amino-oxythionaphthene, and u-isatinanilid are heated with grams of nitrobenzene and 30 grams of bromin for two hours to The further operation is carried out as stated in Example I. The resulting dyestuff forms a brown powder which is very diificul-tly soluble in all of the solvents and which dyes in the alkaline vat wool and cotton brown tints.

Example IV: 10 grams of the condensation-product obtainable from 5-acet-amino phenyl-2 -thioglycol-l-carboxylic acid, or para-amino-oxythionaphthene, and isatin are heated with 150 grams of nitrobenzene and SOgrams of bromin for two hours to 160; After cooling the mass is filtered 0H and the dyestull Washed by boiling it with alco hol. It forms a blackish-brown powder, which dissolves very difficultly in all of the solvents and which dyes W001 and cotton in the alkaline vat reddisl. -a wn-tints.

Example V: 10 grams of the c0ndensation-product obtainable from 5-2LCBlZ9JI1lI10 phenyl 2 thioglycol 1 carboxylic acid, or paraamino-oxythionaphthene, and isatin- 'anilid are heated with 150 grams of nitrobenzene and 30 grains of bromin for 2 hours to 160. The further operation is carried out as indicated in the foregoing example. The new dyestuff forms a blackish -'violet powder which is difiicultly soluble in all of the solvents and which dyes in the alkaline vat wool reddish-blue, cotton bluish gray tints.

Example VI: 10 grams of the condensation-product obtainable from 12 grains of nitroisatin and 10 grams of 6-ainino-3-oxyl-thionaphthene (for instance in presence of acetic acid), or 10 grams of the condensation-product obtainable from 81 grams of meta-acetaminophenylthioglycol ortho-car boxylic acid. and grains of nitroisatin (for instance in presence of acetic-acid-anhydrid), are heated in a reflux apparatus with 10 com. of broinin and 100 com. of: nitrobenzene for about three hours. cooling, the mass is filtered 0E and boiled with alcohol containing some bisulfite. The dyestuti thus obtained forms a brown powder, which is diliicultly soluble in most of the solvents and which dyes in the alkaline vat wool and cotton brownish-yellow tints. If, instead of the said condensationproduct, its reduction-product, obtainable by means of zinc and HCl, hydrosulfite, sodium sulfid or the like, is halogenized, dyestufis are obtained which give similar tints.v

A like result is obtained if, inmanufacturing the primary material, instead of the nitro isatin its reduction-product, the aminodioxindol, is condensed with the meta-aminooxythionaphthene, or with the meta-acetaininophenylthioglycol ortho carboxylic acid and the thus-obtained condensationproducts treated with halogen.

Having now particularly described our invention what we claim is:

1. The herein-described process of making vat-dyestuffs, which consists in treating with a halogen the products inade by con (lensing the amino-oirythionaphthenes with the isatin derivatives, and havingthe gen eral formula:

in which R, means H,acidyl; ltt H, halo gem-N0 N11,; and R :H, halogen.

2. As new products, the herein-described vat dyestuffs, obtainable by halogenizing the products made by condensing the aminooxythionaphthenes with the isatin-derivatives, and having the general formula:

in which R, meansH, acidyl; R H, halogenNO,-, NH and R H, halogen; being brownish to dark powders, insoluble in water, alcohol, benzene, ether, dilute acids and alkalies, soluble in concentrated sulfuric acid with a brownish-violet to blue color, and hardly soluble in hot nitrobenzen-e, anilinand the like, yielding when treated with alkaline reducing agents like hydrosulfite, a yellowish to brown Vat from which cotton and wool are dyed very fast yellowish-brown to brown and grayish tints.

3. As a new product, the vat dyestuif obtainable by treating with halogen the condensation-product of isatin and meta-aminooXythiOnaphthene in'the manner herein de scribed, said product being a r'eddislrbrown powder, insoluble in water, dilute acids and 'alka lies, alcohol, benzene, ether; soluble in concentrated sulfuric acid with a violetbrown color, hardly soluble in hot nitrobene w zene, yielding on treatment with alkaline reducing agents, like hydrosulfite, a yellow vat from which wool and cotton are dyed very fast brown tints.

' In testimony whereof, we our signatures in presence of two witnesses.

ALBRECHT SCHMIDT, ERNST BRYK. ROBERT VOSS. Witnesses:

CARL GRUND, Lnnwic MUELLER. 

